Infrared light emitting device

ABSTRACT

Provided is an infrared light emitting device with high emission intensity. The infrared light emitting device includes: a semiconductor substrate; a first compound semiconductor layer; a light emitting layer containing at least In and Sb and having a predetermined range(s) of Al or Al and Ga proportion(s); a third compound semiconductor layer; and a second compound semiconductor layer containing at least In, Al, and Sb and having a predetermined range(s) of Al or Al and Ga proportion(s), in which the first compound semiconductor layer includes, in the stated order, a first A layer, a first B layer, and a first C layer, each containing at least In and Sb and having a predetermined range(s) of Al or Al and Ga proportion(s), and the proportion(s) of the Al composition or the Al composition and the Ga composition of each layer satisfy a predetermined relation(s).

TECHNICAL FIELD

This disclosure relates to infrared light emitting devices.

BACKGROUND

Generally, infrared rays of a long wavelength band having a wavelength of 2 μm or more are used for human sensors for detecting human bodies, non-contact temperature sensors, gas sensors, and the like, because of its thermal effect and the effect of infrared absorption by a gas. For example, gas sensors can be used for atmospheric environment monitoring and protection, also for early fire detection and the like, and attract attention in recent years. In particular, there are many absorption bands inherent to individual gases in the wavelength range from 2.5 μm to 6.0 μm, which is a wavelength band suitable for use in gas sensors.

The principle of the gas sensors using infrared rays is as follows. For example, when a gas is injected into the space between an infrared light source and an infrared light emitting device, a specific gas absorbs infrared rays having a specific wavelength. Thus, by analyzing the wavelength spectrum before and after the injection of the gas, the type and concentration of the gas can be measured. Here, an incandescent bulb may be used as the infrared light source, for example, and the infrared rays emitted from the incandescent bulb are white light. Therefore, in order to perform spectral analysis of a specific wavelength, it is necessary to provide a filter on the light emitting device side. Such a filter is expensive. In addition, the filter reduces the sensitivity of the gas sensor because it weakens the intensity of infrared rays. Further, the life of an incandescent bulb is short, so it is necessary to frequently replace the light source.

In order to solve the above problem, it is effective to use a semiconductor light emitting diode (LED) which emits infrared rays having a specific wavelength as a light source. Analytical instruments using infrared LEDs can be made smaller, lighter, and lower in power consumption than analytical instruments using other light sources (for example, a light bulb or the like). Infrared LEDs are effective light sources for portable, space-saving applications, and low-power-consumption analytical instrument applications.

However, particularly in the infrared field, analytical instruments using LEDs as light sources have not been widely used at present. One of the reasons is that, for example, known infrared LEDs cannot provide sufficient emission intensity, so that the whole analytical instrument cannot obtain sufficient signal intensity (S/N ratio). When the emission intensity is increased, the S/N ratio increases. Therefore, it is necessary to have sufficient infrared LED emission intensity for wide application.

In infrared LEDs, a so-called pn junction diode structure is formed in which a light emitting layer having a band gap capable of emitting infrared rays with a wavelength of 2 μm or more is sandwiched between an n layer and a p layer, a forward current is passed through the pn junction diode, and electrons and holes are recombined in the light emitting layer to emit infrared rays. AlInSb, which is capable of providing crystals of relatively good quality, is preferably used for infrared LEDs. Examples of the infrared LEDs using AlInSb include one with a structure as described in M. K. Haigh et al., “Mid-Infrared AlxIn1-xSb light-emitting diodes” Applied Physics Letters, 90(23), 23116(2007). However, it is difficult to obtain sufficiently high emission intensity even with this structure.

SUMMARY

It is desired to further improve the emission intensity so that semiconductor light emitting diodes (LED) which emit infrared rays can be subjected to practical use.

In view of these circumstances, it would be helpful to provide an infrared light emitting device with high emission intensity.

The present disclosure provides an infrared light emitting device comprising: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer and containing at least In and Sb, where the light emitting layer has an Al composition at a proportion of n_(light) [%] in all group III elements in the light emitting layer where 0≤n_(light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n₂[%] in all group III elements in the second compound semiconductor layer where 0<n₂<100, and having a film thickness of m₂ [nm] where m₂>2,

wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(1A) [%] in all group III elements in the first A layer where 0<n_(1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(1B) [%] in all group III elements in the first B layer where 0≤n_(1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(1C) [%] in all group III elements in the first C layer where 0≤n_(1C)<18, where n_(1A), n_(1B), n_(1C), n₂, n_(light), m_(1B), and m₂ satisfy the following relations:

|n ₂ −n _(light) |×m ₂ ≤|n _(1B) −n _(1A) |×m _(1B);

n _(1B) >n _(1A) and n _(1B) >n _(1C), or n _(1B) <n _(1A) and n _(1B) <n _(1C); and

n ₂ >n _(light)+5.

The present disclosure also provides an infrared light emitting device comprising: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer, containing at least In and Sb, and having an Al composition at a proportion of n_(Al light) [%] in all group III elements in the light emitting layer and a Ga composition at a proportion of n_(Ga light) [%] in all group III elements in the light emitting layer, where a sum of the proportions n_(Al light) and n_(Ga light) satisfies a relation of 0<n_(Al light)+n_(Ga light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n_(Al2) [%] in all group III elements in the second compound semiconductor layer where 0<n_(Al2)<100 and a Ga composition at a proportion of n_(Ga2) [%] in all group III elements in the second compound semiconductor layer where 0≤n_(Ga2)<100, and having a film thickness of m₂ [nm] where m₂>2,

wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1A) [%] in all group III elements in the first A layer and a Ga composition at a proportion of n_(Ga1A) [%] in all group III elements in the first A layer, where a sum of the proportions n_(Al1A) and n_(Ga1A) satisfies a relation of 0<n_(Al1A)+n_(Ga1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(Al1B)[%] in all group III elements in the first B layer and a Ga composition at a proportion of n_(Ga1B) [%] in all group III elements in the first B layer, where a sum of the proportions n_(Al1B) and n_(Ga1B) satisfies a relation of 0<n_(Al1B)+n_(Ga1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1C) [%] in all group III elements in the first C layer and a Ga composition at a proportion of n_(Ga1C) [%] in all group III elements in the first C layer, where a sum of the proportions n_(Al1C) and n_(Ga1C) satisfies a relation of 0<n_(Al1C)+n_(Ga1C)<18, where n_(Al1A), n_(Ga1A), n_(Al1B), n_(Ga1B), n_(Al1C), n_(Ga1C), n_(Al2), n_(Ga2), n_(Al light), n_(Ga light), m_(1B), and m₂ satisfy the following relations:

|n _(Al2) +n _(Ga2)−(n _(Al light) +n _(Ga light))|×m ₂ ≤|n _(Al1B) +n _(Ga1B)−(n _(Al1A) +n _(Ga1A))|×m _(1B);

n _(Al1B) +n _(Ga1B) >n _(Al1A) +n _(Ga1A) and n _(Al1B) +n _(Ga1B) >n _(Al1C) +n _(Ga1C), or n _(Al1B) +n _(Ga1B) <n _(Al1A) +n _(Ga1A) and n _(Al1B) +n _(Ga1B) <n _(Al1C) +n _(Ga1C);

n _(Al2) +n _(Ga2) >n _(Al light) +n _(Ga light)+5;

0<n _(Ga2)/(n _(Al2) +n _(Ga2))≤1;

0<n _(Ga light)/(n _(Al light) +n _(Ga light))≤1;

0<n _(Ga1A)/(n _(Al1A) +n _(Ga1A))≤1;

0<n _(Ga1B)/(n _(Al1B) +n _(Ga1B))≤1; and

0<n _(Ga1C)/(n _(Al1C) +n _(Ga1C))≤1.

According to the present disclosure, it is possible to provide an infrared light emitting device with high emission intensity.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. 1 is a cross-sectional view illustrating a configuration of an infrared light emitting device according to a first embodiment.

FIG. 2 is a cross-sectional view illustrating a configuration of an infrared light emitting device of a second embodiment.

FIG. 3 is a graph illustrating the measured values of quantum emission efficiency of infrared light emitting devices of Examples 1, 2, 3 and Comparative Examples 1, 2, 3. In the figure, the curve connecting the plots indicates the curve obtained by curve fitting. In the figure, the broken line indicates the value of 75% of the maximum quantum emission efficiency obtained in Example 3, and the arrow indicates the film thickness m₂ (mm) of the second compound semiconductor layer at the intersection of the curve and the broken line.

FIG. 4 is a graph illustrating the measured values of quantum emission efficiency of infrared light emitting devices of Examples 1, 3, 4, 5 and Comparative Examples 4, 5. In the figure, the curve connecting the plots indicates the curve obtained by curve fitting. In the figure, the broken line indicates the value of 75% of the maximum quantum emission efficiency obtained in Example 3, and the arrow indicates the difference in Al composition (%) between the second compound semiconductor layer and the light emitting layer at the intersection of the curve and the broken line.

FIG. 5 illustrates a range in which infrared light emitting devices are considered as having good quantum emission efficiency characteristics.

FIG. 6 illustrates cross-sectional TEM analysis results of three samples of Example 6 and a sample to be compared. The lower row indicates the line defect density (lines/cm²) of the light emitting layer obtained from the results of plane-view TEM analysis conducted on the three samples of Example 6 and the sample to be compared.

FIG. 7 illustrates cross-sectional TEM analysis results of the three samples of Example 6 and the sample to be compared. The lower row indicates the line defect density (lines/cm²) of the light emitting layer obtained from the results of plane-view TEM analysis conducted on the three samples of Example 6 and the sample to be compared.

DETAILED DESCRIPTION

Numerous specific configurations will be described in detail below in order to provide a thorough understanding of embodiments of the present disclosure. It will be apparent, however, that other embodiments may be devised without being limited to the disclosed configurations. In addition, the following embodiments do not limit the aspects and concepts of this disclosure defined by the claims, but include all of the combinations of characteristic configurations described in the embodiments.

<Infrared Light Emitting Device>

The following provides a description of infrared light emitting devices in first and second aspects.

An infrared light emitting device according to the first aspect comprises: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer and containing at least In and Sb, where the light emitting layer has an Al composition at a proportion of n_(light) [%] in all group III elements in the light emitting layer where 0≤n_(light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n₂[%] in all group III elements in the second compound semiconductor layer where 0<n₂<100, and having a film thickness of m₂ [nm] where m₂>2, wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(1A) [%] in all group III elements in the first A layer where 0≤n_(1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(1B) [%] in all group III elements in the first B layer where 0≤n_(1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(1C) [%] in all group III elements in the first C layer where 0≤n_(1C)<18, where n_(1A), n_(1B), n_(1C), n₂, n_(light), m_(1B), and m₂ satisfy the following relations:

|n ₂ −n _(light) |×m ₂ ≤|n _(1B) −n _(1A) |×m _(1B);

n _(1B) >nA and n _(1B) >n _(1C), or n _(1B) <n _(1A) and n _(1B) <n _(1C); and

n ₂ >n _(light)+5.

The reason why the infrared light emitting device cannot obtain sufficient emission intensity is that, for example, the defect density in the vicinity of the second compound semiconductor layer is high so that electrons and holes are deactivated because of non-emission recombination. Examples of main defects in the vicinity of the second compound semiconductor layer include line defects or, in other words, dislocation caused by a difference in lattice constant between the semiconductor substrate and the compound semiconductor material stacked on the substrate. It is known that the dislocation density decreases as the thickness of the compound semiconductor material to be stacked increases. This is mainly because the dislocations collide with each other and disappear. However, increasing the film thickness is not preferable because it requires more film formation time and increases the difficulty of the device formation process. Here, the emission intensity of the infrared light emitting device is proportional to the ratio of emission recombination occurred among the carriers injected into the light emitting layer, that is, the quantum emission efficiency.

The quantum emission efficiency of the infrared light emitting device is lowered due to carrier deactivation caused by the line defects in the vicinity of the second compound semiconductor layer. Therefore, by reducing the line defects in the vicinity of the second compound semiconductor layer, it is possible to improve the quantum emission efficiency.

For the purpose of reducing the line defect density in the vicinity of the second compound semiconductor layer, it is effective to apply a line defect filter layer (for example, in the first aspect, a first B layer containing at least In and Sb and having an Al composition of n_(1B) [%] where 0<n_(1B)<100). The line defect filter layer refers to a layer applied between base materials (for example, in the first aspect, between a first A layer having an Al composition of n_(1A) [%] where 0≤n_(1A)<18 and a first C layer containing at least In and Sb and having an Al composition of n_(1C) [%] where 0≤n_(1C)<18) for the purpose of reducing the line defect density. The line defect filter layer selects a material such that its lattice constant is largely different from that of the base materials, and is thinner than the base materials.

The misfit stress generated by the difference in lattice constant between the base materials and the line defect filter layer is concentrated on the thin line defect filter layer such that the line defects bend in the lateral direction (parallel to the main surface of the semiconductor substrate) in the vicinity of the line defect filter layer. In this respect, when a plurality of bending line defects collide with each other, they disappear. Therefore, by applying a line defect filter layer between base materials, propagation of line defects to the upper layer (the light emitting layer in the first aspect) is suppressed.

In order to improve the quantum emission efficiency of the infrared light emitting device, it is necessary to optimize the compositions and film thicknesses of the materials of the first compound semiconductor layer, the second compound semiconductor layer, and the light emitting layer, respectively. However, it is difficult to theoretically obtain the optimum value, and experimental investigation is required to realize the optimization.

As a result of various investigations, we found that one of the design factors important for improving the quantum emission efficiency of the infrared light emitting device is the relation between (1) the product of the film thickness of the second compound semiconductor layer and the difference in Al composition between the second compound semiconductor layer and the light emitting layer (that is, |n₂−n_(light)|×m₂) and (2) the product of the film thickness of the first B layer and the difference in Al composition between the first B layer and the first A layer (that is, |n_(1B)−n_(1A)|×m_(1B)); specifically, the relation of |n₂−n_(light)|×m₂≤|n_(1B)−n_(1A)|×m_(1B)). It is known that the ease of bending of line defects correlates with the “magnitude” of difference in Al composition. Accordingly, the absolute values are used in the expressions indicative of the difference in Al composition.

Here, if |n₂−n_(light)|×m₂ is sufficiently large, it is expected that the carrier confinement effect to the light emitting layer can be provided by the second compound semiconductor layer, but if |n₂−n_(light)|×m₂>|n_(1B)−n_(1A)|×m_(1B) is satisfied, it was found that line defects penetrating without bending in the vicinity of the first B layer are bent in the lateral direction in the vicinity of the second compound semiconductor layer. In this case, it was found that as the line defect density increases in the vicinity of the second compound semiconductor layer, carrier deactivation via line defects in the vicinity of the second compound semiconductor layer is promoted, and the quantum emission efficiency of the infrared light emitting device decreases.

With the infrared light emitting device of this embodiment, by satisfying|n₂−n_(light)|×m₂≤|n_(1B)−n_(1A)|×m_(1B), bending of line defects occurring in the vicinity of the second compound semiconductor layer is suppressed, which makes it possible to reduce the line defect density in the vicinity of the second compound semiconductor layer. Accordingly, carrier deactivation via line defects in the vicinity of the second compound semiconductor layer is suppressed, and as a result, the quantum emission efficiency of the infrared light emitting device can be maximized.

As the material of the infrared light emitting device, AlInSb capable of providing crystals of relatively good quality can be used. When applying a line defect filter layer (the first B layer in the first aspect) to an infrared light emitting device formed using AlInSb, it is preferable to apply a line defect filter layer containing AlInSb which is the same element type from the viewpoint that the refractive index difference is small and the loss due to internal reflection is small, and from the perspective of ease of the device formation process. By applying an AlInSb layer having a different Al composition from the AlInSb layer of the base materials (the first A layer and the first C layer in the first aspect) as a line defect filter layer, a lattice constant difference and a misfit stress are generated, making it possible to cause line defects to bend.

As used herein, although “on” in the expression “a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type” indicates that a first compound semiconductor layer having the first conductivity type is formed on the semiconductor substrate, it is also included in this expression that there is another layer between the semiconductor substrate and the first compound semiconductor layer having the first conductivity type. The term “on” used in expressing the relationship between other layers has the same meaning.

As used herein, “containing” in the expression “containing at least In and Sb” indicates that In and Sb are contained in the layer, yet this expression also includes cases of containing other elements. Specifically, this expression also includes a case where a slight change is made to the composition of this layer by adding a small amount of other elements (for example, by adding an element such as Al, As, P, Ga, N, or the like by not more than several percent). The term “containing” used in expressing the composition of other layers has the same meaning.

In addition, “in the . . . layer” in the expression “an Al composition at a proportion of . . . in all group III elements in the . . . layer” indicates a range of each corresponding layer, i.e., “in the first compound semiconductor layer having a first conductivity type”, “in the light emitting layer”, “in the third compound semiconductor layer having a second conductivity type”, “in the second compound semiconductor layer”, “in the first A layer”, “in the first B layer”, and “in the first C layer”, respectively, rather than a range of the entire layers described.

Further, from the viewpoint of improving the light extraction efficiency, it is preferable that the infrared light emitting device according to the first aspect emits infrared rays from the semiconductor substrate side rather than from the surface of the semiconductor substrate on which compound semiconductors are deposited where the electrode material is formed.

Hereinafter, each component of the infrared light emitting device according to this embodiment will be described with examples.

<Semiconductor Substrate>

The semiconductor substrate of the infrared light emitting device according to this embodiment is not particularly limited as long as a first compound semiconductor layer having a first conductivity type to be described later can be stacked thereon. Examples of the semiconductor substrate include, but are not limited to, a GaAs substrate, a Si substrate, an InP substrate, and an InSb substrate. From the viewpoint that crystal growth of a compound semiconductor is easy, a GaAs substrate is preferable.

The surface on which the first compound semiconductor layer is formed is referred to as the main surface of the semiconductor substrate.

The semiconductor substrate is not limited by doping with a donor impurity or an acceptor impurity, yet from the viewpoint of enabling a plurality of independent infrared light emitting devices formed on the conductor substrate to be connected in series or in parallel, the semiconductor substrate is desirably semi-insulating or insulatable and separatable from compound semiconductor layers.

From the viewpoint of stacking a compound semiconductor single crystal, the semiconductor substrate is preferably a single crystal substrate. The plane orientation of the semiconductor substrate is not particularly limited, yet for example (001), (111), and (101) are desirable. It is also preferable to use a plane orientation inclined by 1° to 5° with respect to these plane orientations.

The surface of the semiconductor substrate may be heated in a vacuum to remove the oxide film, or a contaminant such as an organic substance or a metal may be removed before the semiconductor substrate is subjected to a cleaning treatment with an acid or an alkali.

<First Compound Semiconductor Layer>

The first compound semiconductor layer of the infrared light emitting device according to this embodiment is formed on the semiconductor substrate and has a first conductivity type (n type, i type, or p type).

In addition, the first compound semiconductor layer having a first conductivity type comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition of n_(1A) [%] where 0≤n_(1A)<18; a first B layer containing at least In and Sb, having an Al composition of n_(1B)[%] where 0≤n_(1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition of n_(1C) [%] where 0≤n_(1C)<18, wherein the following relations are satisfied: n_(1B)>n_(1A) and n_(1B)>n_(1C), or n_(1B)<n_(1A) and n_(1B)<n_(1C).

In addition, the first compound semiconductor layer and a second compound semiconductor layer and a light emitting layer, which will be described later, satisfy|n₂−n_(light)|×m₂≤|n_(1B)−n_(1A)|×m_(1B).

(Measurement Method of Al Composition of Each Layer)

The Al composition of each layer of the first compound semiconductor layer can be obtained as follows by Secondary Ion Mass Spectrometry (SIMS) method. For the measurement, a magnetic field type SIMS apparatus IMS 7f manufactured by CAMECA may be used. In this method, compositional analysis is performed by irradiating a solid surface with beam type primary ion species, digging in the depth direction by means of sputtering phenomenon, and simultaneously detecting the generated secondary ions.

As used herein, the Al composition refers to the ratio of Al element to all group III elements (13 group elements) contained in each layer.

Specifically, cesium ion (Cs+) is used as the primary ion species, the primary ion energy is set to 2.5 keV, and the beam incident angle is set to 67.2°. Under these conditions, MCs+ (M is Al, Ga, In, As, Sb, or the like) with a small matrix effect can be detected as the secondary ion species to be detected.

At this time, sputtering is carried out under the above-mentioned conditions and up to the depth of the target layer for a predetermined period of time to analyze the composition of the target layer. The depth of the target layer can be obtained from the thickness of each layer by cross sectional TEM measurement as described later. For the sputtering time-depth conversion in SIMS analysis, sputtering rate is obtained by measuring the sputtering depth for a certain period of time under the same condition as the analysis by using, for example, a stylus profilometer, and used to convert the sputtering time at the time of sample measurement into depth.

Then, from the signal intensity of MCs+ in each layer, the Al composition was obtained. For example, in the case of an AlInSb layer, the Al composition was obtained from: (signal intensity of AlCs+)/((signal intensity ofAlCs+)+(signal intensity of InCs+)).

Even if each layer has a uniform composition in the depth direction, the signal intensity sometimes distributes in the depth direction due to the influence of sputtering. In this case, the signal intensity of each layer is represented by the maximum signal intensity.

Note that the quantitative value of the Al composition obtained by the analysis can be accompanied by deviation from the true value. In order to correct this deviation from the true value, a separate sample for which the lattice constant value obtained from the X-ray diffraction (XRD) method has been obtained is prepared, and, using this sample as a standard sample whose Al composition value is already known, SIMS analysis is performed under the measurement conditions for the Al composition of each layer of the first compound semiconductor layer, and the sensitivity coefficient of the Al composition with respect to the signal intensity can be obtained. The Al composition of each layer of the first compound semiconductor layer can be obtained by multiplying the SIMS signal intensity in each layer of the first compound semiconductor layer by the sensitivity coefficient.

In this case, as a separate sample, Al_(x)In_(1-x)Sb having a film thickness of 800 nm stacked on a GaAs substrate can be used. For this sample, a lattice constant may be obtained by X-ray diffraction (XRD) method using an X-ray diffractometer X′Pert MPD manufactured by Spectris Co., Ltd., as described below to determine the Al composition x as a standard sample.

By performing 2θ-ω scan by X-ray diffraction, the lattice constant in the direction normal to the substrate surface of the first A layer can be obtained from the peak position in the 2θ-ω scan of the plane index of the plane corresponding to the plane orientation of the substrate surface, and the Al composition x can be determined from the lattice constant in the normal direction using the Vegard's rule. In this case, it is assumed that there is no anisotropic distortion of the Al_(x)In_(1-x)Sb layer. Specifically, the Vegard's rule is represented by:

a _(AlInSb) =xa _(AlSb)+(1−x)a _(InSb)  Expression (1)

Where a_(AlSb) is the lattice constant of AlSb, a_(InSb) is the lattice constant of InSb, and a_(AlInSb) is the lattice constant of the Al_(x)In_(1-x)Sb layer obtained by the above-described X-ray diffraction. For a_(AlSb), 6.1355 Å may be used and 6.4794 Å for a_(InSb).

As a standard sample for SIMS measurement, a sample with 0.10<x<0.15 may be used.

(Measurement Method of Composition of Elements Other than Al in Each Layer)

The composition of elements other than Al in each layer of the first compound semiconductor layer can also be measured by using the same method as described above.

For example, the Ga composition in the case of containing Ga can also be measured by using the same method as described above.

In this case, Ga_(g)In_(1-g)Sb having a film thickness of 800 nm stacked on a GaAs substrate is used as a separate sample. Using Ga_(g)In_(1-g)Sb, the Vegard's rule is specifically expressed by:

a _(GaInSbg) =ga _(GaSb)+(1−g)a _(InSb)  Expression (2)

Where a_(GaSb) is the lattice constant of GaSb, a_(InSb) is the lattice constant of InSb, and a_(GaInSb) is the lattice constant of Al_(g)In_(1-g)Sb obtained by the above-described X-ray diffraction. We used 6.0959 Å for a_(GaSb) and 6.4794 Å for a_(InSb). As a standard sample for SIMS measurement, a sample with 0.10<g<0.15 was used.

The composition of elements other than Al in each layer other than the first compound semiconductor layer can also be measured by using the same measurement method.

(Measurement Method of Film Thickness of Each Layer)

The film thickness of each layer of the first compound semiconductor layer can be measured by cross-sectional TEM (Transmission Electron Spectroscopy) method. Specifically, a sample having a thickness of about 500 nm or less was prepared by FIB method using an FIB apparatus (FB-2100) manufactured by Hitachi High-Technologies Corporation, sectional images were observed in transmission images at an acceleration voltage of 200 kV using an STEM apparatus (HD-2300A) manufactured by Hitachi, Ltd., and the thickness of each layer was measured. The film thicknesses of the layers other than the first compound semiconductor layer can also be measured by using the same measurement method.

From the viewpoint of applying the stress necessary for bending of line defects, the lower limit of the film thickness m_(1A) [nm] of the first A layer is preferably 2 nm or more, and more preferably 5 nm or more.

For the film thickness m_(1A) of the first A layer, from the viewpoint of absorbing the misfit stress, it is preferable that m_(1A)≥200 nm, and more preferable that m_(1A)≥300 nm. The same range is also preferable for the film thickness m_(1C) of the first C layer.

Further, from the viewpoints of increase in the film formation time and ease of the device formation process, it is preferable that m_(1A)≤700 nm, and particularly preferable that m_(1A)≤600 nm. The same range is also preferable for m_(1C).

From the viewpoint of improving the emission intensity in the 3.3 μm band, the Al composition n_(1A) of the first A layer is preferably 8 or more, and more preferably 9 or more. From the same viewpoint, it is preferably 12 or less, and more preferably 11 or less. Similarly, the Al composition n_(1C) of the first C layer is preferably 8 or more, and more preferably 9 or more. Similarly, it is preferably 12 or less, and more preferably 11 or less. As a result, the lattice constant difference from the light emitting layer is reduced, and the crystallinity of the light emitting layer can be improved. Since this wavelength band overlaps with the absorption wavelength band of methane, it is suitable as an infrared light emitting device for a methane gas sensor.

From the viewpoint of improving the emission intensity in the 4.3 μm band, the Al composition n_(1A) of the first A layer is preferably 4 or more, and more preferably 5 or more. From the same viewpoint, it is preferably 8 or less, and more preferably 7 or less. Similarly, the Al composition n_(1C) of the first C layer is preferably 4 or more, and more preferably 5 or more. Similarly, it is preferably 8 or less, and more preferably 7 or less. As a result, the lattice constant difference from the light emitting layer is reduced, and the crystallinity of the light emitting layer can be improved. Since this wavelength band overlaps with the absorption wavelength band of CO₂, it is suitable as an infrared light emitting device for a CO₂ gas sensor.

From the viewpoint of uniformly applying stress to the first B layer, it is preferable that |n_(1A)−n_(1C)|<10, and more preferable that |n_(1A)−n_(1C)|<3.

From the viewpoint of reducing crystal defects, it is preferable that the Al composition n_(1A) of the first A layer, the Al composition n_(1C) of the first C layer, and the Al composition n_(light) of the light emitting layer are the same.

It is preferable that the first compound semiconductor layer has a layered structure in which a first A layer, a first B layer, and a first C layer are sequentially stacked on top of one another in the stated order for a number of repetitions i. Specifically, in the layered structure, the first A layer₍₁₎→the first B layer₍₁₎→the first C layer₍₁₎→the first A layer₍₂₎→the first B layer₍₂₎→the first C layer₍₂₎→ . . . →the first A layer_((i))→the first B layer_((i))→the first C layer_((i))→ . . . and so on are stacked on top of each other in the stated order. In this case, the composition and film thickness are preferably the same for the first A layers_((k)) (k=1, 2, . . . , i). Similarly, the composition and film thickness are preferably the same for the first B layers_((k)) (k=1, 2, . . . , i). Similarly, the composition and film thickness are preferably the same for the first C layers_((k)) (k=1, 2, . . . , i). Also, the compositions of the first C layer_((k)) and the first A layer_((k+1)) are preferably the same. In addition, the first C layer_((k)) and the first A layer_((k+1)) may be integrated.

In this case, the number of repetitions i is preferably i≥2, and more preferably i≥3 from the viewpoint of reducing the line defect density.

From the viewpoints of increase in the film formation time and ease of the device formation process, it is preferable that i≤6, and more preferable that i≤5.

Besides the above-mentioned layered structure in which first A layers, first B layers, and first C layers are stacked in the stated order, examples of the material of the first compound semiconductor layer may include AlAs, GaAs, InAs, AlSb, GaSb, InSb, or InP alone, a single layer of a mixed crystal thereof, or a layered structure thereof.

In the case where the above-described semiconductor substrate is a GaAs substrate, a layer in contact with the GaAs substrate in the first compound semiconductor layer is preferably an InSb layer. In other words, it is preferable that the first A layer closest to the GaAs substrate in the first compound semiconductor layer is formed in contact with the InSb layer.

The first compound semiconductor layer is preferably n- or p-type doped with a donor impurity or an acceptor impurity, but it may not necessarily be doped as long as it has a first conductivity type. In the case where the first compound semiconductor layer is doped, the doping concentration is preferably 1×10¹⁸ [cm⁻³] or more from the viewpoint of reducing the contact resistance with the metal (electrode), and it is desirably 1×10¹⁹ [cm⁻³] or less from the viewpoint of securing crystallinity.

The first conductivity type is preferably of n-conductivity type from the viewpoint of current diffusion of the infrared light emitting device and improvement of infrared transmittance by the Burstein-Moth effect.

<Second Compound Semiconductor Layer>

The second compound semiconductor layer of the infrared light emitting device according to this embodiment is formed on the first compound semiconductor layer and has an n-, i-, or p-conductivity type.

The second compound semiconductor layer contains at least In, Al, and Sb, has an Al composition of n₂[%] (0<n₂<100), a film thickness of m₂ [nm] (m₂>2), and satisfies a relation of n₂>n_(light)+5.

Here, as illustrated in FIGS. 3 and 4, when the film thickness is m₂ [nm] (m₂>2) and the Al composition n₂ satisfies a relation of n₂>n_(light)+5, it is possible to realize a sufficient carrier confinement effect to the light emitting layer. From the viewpoint of suppressing the decrease in quantum emission efficiency, which is caused by the injected carrier diffusion generated as a result of n₂ being too small, to be 25% or less as compared to the case where n₂ is the optimum value, it is more preferable that n₂>n_(light)+7 and that m₂ is 5 nm or more in view of the lower limits of n₂ and m₂ in FIGS. 3 and 4.

Further, from the viewpoint of suppressing the decrease in quantum emission efficiency, which is caused by a line defect penetrating the first B layer bending in the vicinity of the second compound semiconductor layer, to be 25% or less as compared to the case where |n₂−n_(light)|×m₂ is the optimum value, it is preferable to satisfy a relation of |n₂−n_(light)|×m₂≤441 in view of the product of the upper limit of n₂ and the upper limit of m₂ in FIGS. 3 and 4.

The material of the second compound semiconductor layer is not particularly limited as long as it is a compound semiconductor containing at least In and Sb and has an Al composition that satisfies n_(light) [%] (0≤n_(light)<100).

As can be seen from FIGS. 3 and 4, in terms of obtaining favorable quantum emission efficiency, m₂ is preferably 5 nm to 21 nm, and more preferably 6 nm to 18 nm, and the difference in Al composition between the second compound semiconductor layer and the light emitting layer is preferably 7% to 21%, and more preferably 8% to 14%.

<Light Emitting Layer>

The light emitting layer in the infrared light emitting device according to this embodiment is formed on the second compound semiconductor layer, contains at least In and Sb, and has an Al composition of n_(light) [%] (0≤n_(light)<18).

From the viewpoint of improving the emission intensity in the 3.3 μm band, the Al composition n_(light) of the light emitting layer is preferably 8 or more, and more preferably 9 or more. From the same viewpoint, it is preferably 12 or less, and more preferably 11 or less. Since this wavelength band overlaps with the absorption wavelength band of methane, it is suitable as an infrared light emitting device for a methane gas sensor.

From the viewpoint of improving the emission intensity in the 4.3 μm band, the Al composition n_(light) of the light emitting layer is preferably 4 or more, and more preferably 5 or more. From the same viewpoint, it is preferably 8 or less, and more preferably 7 or less. Since this wavelength band overlaps with the absorption wavelength band of CO₂, it is suitable as an infrared light emitting device for a CO₂ gas sensor.

The material of the light emitting layer is not particularly limited as long as it is a compound semiconductor having a band gap corresponding to infrared rays having a wavelength of 2 μm or more.

The conductivity type of the light emitting layer may be n type, i type, or p type. As for doping, the light emitting layer may be non-doped (that is, it does not contain impurities), or may be n- or p-type doped with a donor impurity or an acceptor impurity.

From the viewpoint of preventing overflow of electrons and holes at the time of voltage application, the lower limit of the film thickness of the light emitting layer is preferably 10 nm or more, and more preferably 20 nm or more.

The upper limit of the film thickness of the light emitting layer is preferably 4000 nm or less, and more preferably 3000 nm or less, from the viewpoints of increase in the film formation time and ease of the device formation process.

<Layer Having Second Conduction Type>

The layer having a second conductivity type of the infrared light emitting device according to this embodiment is formed on the light emitting layer and has a second conductivity type (n type, i type, or p type).

It is preferable that the layer having a second conductivity type has a conductivity type opposite to that of the first conductivity type of the first compound semiconductor layer. For example, if the first compound semiconductor layer is of n type, the layer having a second conductivity type is preferably of p type, and if the first compound semiconductor layer is of p type, the layer having a second conductivity type is preferably of n type.

As described above, since it is preferable that the first compound semiconductor layer be of n type, the layer having a second conductivity type is preferably of p type.

The layer having a second conductivity type is preferably n- or p-type doped with a donor impurity or an acceptor impurity, but it may not necessarily be doped as long as it has a second conductivity type.

In the case where the layer having a second conductivity type is doped, the doping concentration is preferably 1×10¹⁸ [cm⁻³] or more from the viewpoint of reducing the contact resistance with the metal (electrode), and it is preferably 1×10¹⁹ [cm⁻³] or less from the viewpoint of securing crystallinity.

The material of the layer having a second conductivity type is not particularly limited as long as it is a compound semiconductor. Examples thereof may include AlAs, GaAs, InAs, AlSb, GaSb, InSb, or InP alone, a single layer of a mixed crystal thereof, or a layered structure thereof.

In the case where the layer having a second conductivity type is in direct contact with the light emitting layer, the material of the layer in contact with the light emitting layer in the layer having a second conductivity type is preferably a material having a larger band gap than the light emitting layer from the viewpoint of improving the carrier confinement effect to the light emitting layer.

From the viewpoint of preventing damage during the device formation process, the lower limit of the film thickness [nm] of the layer having a second conductive type is preferably 30 nm or more, and more preferably 50 nm or more. The upper limit of the film thickness [nm] of the layer having a second conductivity type is preferably 2000 nm or less, and more preferably 1000 nm or less, from the viewpoints of increase in the film formation time and ease of the device formation process.

From the viewpoint of improving the carrier confinement effect to the light emitting layer, the second compound semiconductor layer is preferably formed in both of regions between the light emitting layer and the third compound semiconductor layer and between the first compound semiconductor layer and the light emitting layer.

In an embodiment of the present disclosure, each of the compound semiconductor layers (for example, the first compound semiconductor layer, the light emitting layer, and the second compound semiconductor layer) can be formed by using various film forming methods. For example, preferable methods are a molecular beam epitaxy (MBE) method and a metal organic vapor phase epitaxy (MOVPE) method. Each of these methods can be used to form each compound semiconductor layer on the semiconductor substrate. In the step of forming each compound semiconductor layer, the semiconductor substrate may be once taken out from the film forming apparatus into the atmosphere during the formation of each layer constituting the corresponding compound semiconductor layer.

<Layered Structure>

In an embodiment of the present disclosure, the infrared light emitting device has the following layered structure. A first compound semiconductor layer 20 comprises a structure in which at least a first A layer, a first B layer, and a first C layer according to claim 1 are stacked on top of one another in the stated order.

In this case, the first B layer functions as a line defect filter layer, and the first A layer and the first C layer function as a buffer layer that absorbs the misfit stress. By giving a misfit stress to the first B layer, line defects are caused to bend at the interfaces between the first A layer and the first B layer and between the first B layer and the first C layer.

Therefore, as the differences in Al composition between the first B layer and the first A layer and between the first B layer and the first C layer become larger, the misfit stress becomes larger such that line defects are caused to bend more easily. On the other hand, if the differences in Al composition between the first B layer and the first A layer and between the first B layer and the first C layer become too large, the crystal cannot withstand such excessively large misfit stress, and conversely line defects occur.

Further, as the film thickness m_(1B) of the first B layer becomes thicker, the misfit stress increases, and line defects bend more easily. On the other hand, if the film thickness m_(1B) of the first B layer is too large, the misfit stress becomes so large that the crystal cannot withstand the stress, and conversely line defects occur.

The difference in Al composition between the first B layer and the first A layer, the difference in Al composition between the first B layer and the first C layer, and the film thickness m_(1B) of the first B layer are not independent from one another, and there are suitable ranges.

A second compound semiconductor layer 30 provides the carrier confinement function to the light emitting layer as described above if the following relations are satisfied:

m ₂>2; and

n ₂ >n _(light)+5.

On the other hand, as the difference in Al composition between the second compound semiconductor layer and the light emitting layer becomes larger, line defects penetrating through the first compound semiconductor layer without bending and reaching the second compound semiconductor layer bend more easily in the vicinity of the second compound semiconductor layer, carrier deactivation via these line defects in the vicinity of the second compound semiconductor layer is promoted, and the quantum emission efficiency of the infrared light emitting device is lowered.

Further, as the film thickness m₂ of the second compound semiconductor layer is increased, line defects penetrating through the first compound semiconductor layer without bending and reaching the second compound semiconductor layer bend more easily in the vicinity of the second compound semiconductor layer, carrier deactivation via these line defects in the vicinity of the second compound semiconductor layer is promoted, and the quantum emission efficiency of the infrared light emitting device is lowered.

The difference in Al composition between the second compound semiconductor layer and the light emitting layer, the difference in Al composition between the first B layer and the first A layer, and the film thickness m₂ of the second compound semiconductor layer are not independent from each other, and there are suitable ranges as described above.

The following describes embodiments of the disclosure with reference to the drawings. However, in the drawings described below, the same reference numerals are given to the corresponding portions, and the description thereof will be omitted as appropriate in the overlapping portions. The embodiments of the present disclosure are merely illustrative of a configuration for embodying the technical idea of the disclosure, but are not intended to limit the material, shape, structure, arrangement, dimension, and the like of each portion to those disclosed herein. In addition, the embodiments of the present disclosure include all of the combinations of characteristic configurations described herein. Various modifications can be made to the technical idea of the present disclosure within the technical scope defined by the claims.

Hereinafter, first and second embodiments of the infrared light emitting device according to the first aspect will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view illustrating the configuration of a first embodiment of the infrared light emitting device 100 according to the disclosure. The infrared light emitting device 100 has a structure in which a compound semiconductor layer 60 is stacked on a semiconductor substrate 10.

The compound semiconductor layer 60 has a structure in which a first compound semiconductor layer 20, a second compound semiconductor layer 30, a light emitting layer 40, and a layer 50 having a second conductivity type are stacked on top of one another in the stated order. In the first embodiment, the first compound semiconductor layer 20 comprises a first A layer 22 containing at least In and Sb and having an Al composition of n_(1A) [%] (0≤n_(1A)<18). In addition, the first compound semiconductor layer 20 comprises a first B layer 23 containing at least In and Sb and having an Al composition of n_(1B) [%] (0≤n_(1B)<100). In addition, the first compound semiconductor layer 20 comprises a first C layer 24 containing at least In and Sb and having an Al composition of n_(1C) [%] (0≤n_(1C)<18). In the first embodiment, the first compound semiconductor layer 20 has a structure in which a set of layers, namely a first A layer, a first B layer, and a first C layer are stacked in the stated order.

In this case, the first compound semiconductor layer 20 further comprises a layer containing InSb (InSb layer 21). As illustrated in FIG. 1, the first compound semiconductor layer 20 has a structure in which the first A layer 22 is stacked directly on the InSb layer 21. Further, in the first embodiment, the infrared light emitting device 100 has a structure in which the second compound semiconductor layer is stacked directly on the first C layer.

FIG. 2 is a cross-sectional view illustrating the configuration of a second embodiment of the infrared light emitting device 100 according to the disclosure. In the second embodiment, the first compound semiconductor layer 20 has a structure where the number of repetitions i for the above layered structure is 2. In FIG. 2, the same reference numerals are given to the same components as those of the first embodiment of the infrared light emitting device 100, and the description thereof will be omitted.

In the second embodiment, the first compound semiconductor layer 20 comprises a first D layer 25 containing at least In and Sb and having an Al composition of n_(1D) [%] (0≤n_(1D)<100). In addition, the first compound semiconductor layer 20 comprises a first E layer 26 containing at least In and Sb and having an Al composition of n_(1E) [%] (0≤n_(1E)<18). In the second embodiment, the infrared light emitting device 100 has a structure in which the second compound semiconductor layer is stacked directly on the first E layer.

Although the first and second embodiments of the present disclosure have been described above, the technical scope of the disclosure is not limited to the scope disclosed herein. For example, the number of repetitions i for the layered structure is not limited to 2, and may be selected within the range of 3 to 6. It will be readily apparent to those skilled in the art that various modifications or improvements can be added to the above embodiments. It will be appreciated that the claims cover all such modifications or improvements as fall within the technical scope of the present disclosure.

Hereinafter, the infrared light emitting device according to the second aspect will be described.

An infrared light emitting device according to the second aspect comprises: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer, containing at least In and Sb, and having an Al composition at a proportion of n_(Al light) [%] in all group III elements in the light emitting layer and a Ga composition at a proportion of n_(Ga light) [%] in all group III elements in the light emitting layer, where a sum of the proportions n_(Al light) and n_(Ga light) satisfies a relation of 0<n_(Al light)+n_(Ga light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n_(Al2) [%] in all group III elements in the second compound semiconductor layer where 0≤n_(Al2)<100 and a Ga composition at a proportion of n_(Ga2) [%] in all group III elements in the second compound semiconductor layer where 0<n_(Ga2)<100, and having a film thickness of m₂ [nm] where m₂>2, wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1A) [%] in all group III elements in the first A layer and a Ga composition at a proportion of n_(Ga1A) [%] in all group III elements in the first A layer, where a sum of the proportions n_(Al1A) and n_(Ga1A) satisfies a relation of 0<n_(Al1A)+n_(Ga1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(Al1B) [%] in all group III elements in the first B layer and a Ga composition at a proportion of n_(Ga1B) [%] in all group III elements in the first B layer, where a sum of the proportions n_(Al1B) and n_(Ga1B) satisfies a relation of 0<n_(Al1B)+n_(Ga1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1C) [%] in all group III elements in the first C layer and a Ga composition at a proportion of n_(Ga1C) [%] in all group III elements in the first C layer, where a sum of the proportions n_(Al1C) and n_(Ga1C) satisfies a relation of 0<n_(Al1C)+n_(Ga1C)<18, where n_(Al1A), n_(Ga1A), n_(Al1B), n_(Ga1B), n_(Al1C), n_(Ga1C), n_(Al2), n_(Ga2), n_(Al light), n_(Ga light), m_(1B), and m₂ satisfy the following relations:

|n _(Al2) +n _(Ga2)−(n _(Al light) +n _(Ga light))|×m ₂ ≤|n _(Al1B) +n _(Ga1B)−(n _(Al1A) +n _(Ga1A))|×m _(1B);

n _(Al1B) +n _(Ga1B) >n _(Al1A) +n _(Ga1A) and n _(Al1B) +n _(Ga1B) >n _(Al1C) +n _(Ga1C), or n _(Al1B) +n _(Ga1B) <n _(Al1A) +n _(Ga1A) and n _(Al1B) +n _(Ga1B) <n _(Al1C) +n _(Ga1C); and

n _(Al2) +n _(Ga2) >n _(Al light) +n _(Ga light)+5.

In the infrared light emitting device according to the first aspect, the proportion of the Al composition of each layer containing Al is defined, whereas in the infrared light emitting device according to the second aspect, the sum of the proportion of the Al composition of each layer containing Al and the proportion of the Ga composition is defined.

Further, the infrared light emitting device according to the second aspect also satisfies the following conditions:

0<n _(Ga2)/(n _(Al2) +n _(Ga2))≤1,

0<n _(Ga light)/(n _(Al light) +n _(Ga light))≤1,

0<n _(Ga1A)/(n _(Al1A) +n _(Ga1A))≤1,

0<n _(Ga1B)/(n _(Al1B) +n _(Ga1B))≤1, and

0<n _(Ga1C)/(n _(Al1C) +n _(Ga1C))≤1.

The infrared light emitting device according to this aspect may also improve the emission intensity by increasing the quantum emission efficiency. Since GaxIn_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb obtained by replacing all or some of the Als in Al_(x)In_(1-x)Sb with Ga has a lattice constant close to that of Al_(x)In_(1-x)Sb and can generate a stress equivalent to that of Al_(x)In_(1-x)Sb, it can be used as the material of the line defect filter layer instead of Al_(x)In_(1-x)Sb.

Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb can also be used as the material of the second compound semiconductor layer because adjustment of x and y can also provide the function of suppressing the diffusion current similarly to Al_(x)In_(1-x)Sb. As described above, since Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb has a lattice constant close to that of Al_(x)In_(1-x)Sb and generates a stress equivalent to that of Al_(x)In_(1-x)Sb, carrier deactivation occurs through line defects bent in the vicinity of the second compound semiconductor even when Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb is used for the second compound semiconductor layer.

The effect of the present disclosure can be also exhibited in the case of Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb obtained by replacing all or some of the Als in Al_(x)In_(1-x)Sb with Ga.

The emission intensity, the quantum emission efficiency, the action and effect of the disclosure, and the like of the infrared light emitting device according to the second aspect may be the same as those described for the infrared light emitting device according to the first aspect.

Each component of the infrared light emitting device according to the second aspect may be configured as follows. That is, the semiconductor substrate may be configured as in the first aspect. The first compound semiconductor layer, the second compound semiconductor layer, the light emitting layer, and the third compound semiconductor layer having a second conductivity type may be configured as in the first aspect, except that the proportion of the Al composition of each layer containing Al is defined in the first aspect, whereas the sum of the proportion of the Al composition of each layer containing Al and the proportion of the Ga composition is defined in the second aspect as described above. Here, the Al composition of each layer, the composition of elements other than Al in each layer, and the film thickness of each layer may be measured in the same way as in the first aspect. Further, the layered structure of the infrared light emitting device may be the same as in the first aspect.

EXAMPLES

The present disclosure is described in detail below based on examples. However, this disclosure is not limited to the following examples. Of course, various modifications are possible without departing from the gist of the disclosure.

Example 1

As illustrated in FIG. 2, the following layers were stacked in the stated order on a semi-insulating GaAs substrate (a semiconductor substrate 10) using an MBE apparatus to form a compound semiconductor layer 60:

an n-type InSb layer 21 doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.5 μm; an n-type Al_(0.08)In_(0.92)Sb layer (a first A layer 22) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.5 μm; an n-type Al_(0.30)In_(0.70)Sb layer (a first B layer 23) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.02 μm; an n-type Al_(0.08)In_(0.92)Sb layer (a first C layer 24) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.5 μm; an n-type Al_(0.30)In_(0.70)Sb layer (a first D layer 25) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.02 μm; an n-type Al_(0.08)In_(0.92)Sb layer (a first E layer 26) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.5 μm; an n-type Al_(0.30)In_(0.70)Sb layer (a second compound semiconductor layer 30) doped with Sn at 7×10¹⁸ [cm⁻³] to a thickness of 0.02 μm; a non-doped Al_(0.08)In_(0.92)Sb layer (a light emitting layer 40) to a thickness of 1 μm; a p-type Al_(0.30)In_(0.70)Sb layer (a third compound semiconductor layer having a second conductivity type) doped with Zn at 3×10¹⁸ [cm⁻³] to a thickness of 0.02 μm; and a p-type Al_(0.08)In_(0.92)Sb layer (a layer 50 having a second conductivity type) doped with Zn at 3×10¹⁸ [cm⁻³] to a thickness of 0.5 μm.

Then, a resist pattern was formed on the compound semiconductor layer 60, and etching was performed to fabricate a mesa structure. Further, insulating grooves made of silicon oxide were formed between the mesa structures such that the respective light emitting devices were electrically independent, and silicon nitride was formed as an insulating layer on the entire surface of the compound semiconductor layer 60 including the mesa structure and insulating groove. A contact hole was formed in a part of the insulating layer, and titanium (Ti), platinum (Pt), and gold (Au) were deposited in the stated order so as to cover the contact hole to form an electrode portion, whereby a plurality of serially-connected infrared light emitting devices were obtained.

Examples 2 to 5

According to Table 1, the Al composition n₂ and film thickness m₂ were changed for each second compound semiconductor layer 30.

TABLE 1 |n_(1B) − |n_(1B) − |n₂ − |n₂ − n_(1A) n_(1B) n_(1C) m_(1B) n_(1A)| n_(1A)| × m₂ n₂ n_(light)| n_(light)| × Example (%) (%) (%) (nm) (%) m_(1B) (nm) (%) (%) m₂ 1 8 30 8 20 22 440 20 30 22 440 2 8 30 8 20 22 440 6 30 22 132 3 8 30 8 20 22 440 10 30 22 220 4 8 30 8 20 22 440 20 19 11 220 5 8 30 8 20 22 440 20 23 15 300

Comparative Examples 1 to 5

According to Table 2, the Al composition n₂ and film thickness m₂ were changed for each second compound semiconductor layer 30.

TABLE 2 Compar- |n_(1B) − |n_(1B) − |n₂ − |n₂ − ative n_(1A) n_(1B) n_(1C) m_(1B) n_(1A)| n_(1A)| × m₂ n₂ n_(light)| n_(light)| × Example (%) (%) (%) (nm) (%) m_(1B) (nm) (%) (%) m₂ 1 8 30 8 20 22 440 2 30 22 44 2 8 30 8 20 22 440 30 30 22 660 3 8 30 8 20 22 440 40 30 22 880 4 8 30 8 20 22 440 20 13 5 100 5 8 30 8 20 22 440 20 33 25 500 <Measurements of Al Composition and Measurement of Composition of Elements other than Al of Each Layer>

The Al composition of each layer was measured by a secondary ion mass spectrometry (SIMS) method using a magnetic field type SIMS apparatus IMS 7f manufactured by CAMECA. Specifically, cesium ion (Cs+) was used as the primary ion species, the primary ion energy was set to 2.5 keV, and the beam incident angle was set to 67.2°. Under these conditions, MCs+(M is Al, Ga, In, As, Sb, or the like) with a small matrix effect was detected as the secondary ion species to be emitted.

Measurement of the Al composition of each layer was performed using Al_(x)In_(1-x)Sb having a film thickness of 800 nm stacked on a GaAs substrate as a replacement sample, and for this sample, the lattice constant was measured by X-ray diffraction (XRD) using an X-ray diffractometer X′Pert MPD manufactured by Spectris Co., Ltd. Details of the measurement of the Al composition of each layer were as described in the Detailed Description section. The composition of elements other than Al in each layer was measured in accordance with the measurement of the Al composition of each layer described above. Details of the measurement of the composition of elements other than Al in each layer were as described in the Detailed Description section.

<Comparison of Quantum Emission Efficiency>

Quantum emission efficiency was measured for the infrared light emitting devices formed in Examples 1 to 5 and Comparative Examples 1 to 5. Specifically, the emission intensity when applying a current of 10 mA in the forward direction to each of the devices obtained in the examples and comparative examples was measured, the obtained emission intensity was converted into the value of emission intensity per injected current density, that is, the quantum emission efficiency, and the value was taken as the quantum emission efficiency of the infrared light emitting device.

It was confirmed that high quantum emission efficiency could be obtained in the conditions of Examples 1 to 5 in which m₂ and n₂ satisfied the following relations as compared with Comparative Examples 1 to 5:

|n ₂ −n _(light) |×m ₂ ≤|n _(1B) −n _(1A) |×m _(1B);

n _(1B) >n _(1A) and n _(1B) >n _(1C), or n _(1B) <n _(1A) and n _(1B) <n _(1C); and

n ₂ >n _(light)+5.

Referring now to FIG. 5, Examples 1 to 5 are compared with Comparative Examples 1 to 5, and the above relations are further investigated. The horizontal axis in FIG. 5 indicates the film thickness m₂ [nm] of the second compound semiconductor layer 30. The vertical axis in FIG. 5 indicates the difference in Al composition [%] between the second compound semiconductor layer 30 and the light emitting layer 40. As described above, it is important to satisfy n₂>n_(light)+5 in order to prevent the injected carrier diffusion which would otherwise cause a deterioration in emission intensity, and furthermore, it is preferable that m₂>2 is satisfied. First, in FIG. 5, m₂>2 is satisfied in a region on the right side of a straight line 1100. The magnitude [%] of difference in Al composition between the second compound semiconductor layer 30 and the light emitting layer 40 is |n₂−n_(light)|. That is, in FIG. 5, in a region above a straight line 1101, a relation of n₂>n_(light)+5 is satisfied.

Further, in order to prevent line defects penetrating through the first B layer from bending in the vicinity of the second compound semiconductor layer, it is preferable to satisfy a relation of |n₂−n_(light)|×m₂<440. In FIG. 5, a relation of |n₂−n_(light)|×m₂≤440 is satisfied within the range not going beyond a curve 1102. In order to prevent the diffusion current and to prevent line defects penetrating through the first B layer from bending in the vicinity of the second compound semiconductor layer, the infrared light emitting device 100 preferably has a configuration such that it falls within a region 110 surrounded by the straight line 1100, the straight line 1101, and the curve 1102. The region 110 does not include points on the straight line 1100 and the straight line 1101, but includes points on the curve 1102. As illustrated in FIG. 5, Examples 1 to 5 fall within the region 110. In contrast, Comparative Examples 1 to 5 are out of the region 110.

Preferably, the infrared light emitting device 100 included in the region 110 further has a predetermined relationship with the characteristics of the line defect filter in the first B layer such that line defects do not bend in the vicinity of the second compound semiconductor layer. In other words, it is preferable to satisfy, like a line defect filter, a relational expression indicating that line defects are prevented from bending in the vicinity of the second compound semiconductor layer. According to the above investigation, this expression is represented by |n₂−n_(light)|×m₂≤|n_(1B)−n_(1A)|×m_(1B). As confirmed again with reference to FIG. 5, the infrared light emitting device 100 of Examples 1 to 5 satisfying the above relational expression can obtain high quantum emission efficiency and can further improve the emission intensity.

Example 6

The following layers were stacked in the stated order on a semi-insulating GaAs substrate to form a compound semiconductor layer: an InSb layer to a thickness of 0.5 μm; a first compound semiconductor layer (a first A layer): an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm; a line defect filter layer (a first B layer) to be described later to a thickness of 0.02 μm; a first compound semiconductor layer (a first C layer): an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm; a line defect filter layer (a first D layer) to be described later: Al_(0.3)In_(0.7)Sb layer to a thickness of 0.02 μm; a first compound semiconductor layer (a first E layer): an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm; a second compound semiconductor layer: an Al_(0.3)In_(0.7)Sb layer to a thickness of 0.02 μm; a light emitting layer: an Al_(0.08)In_(0.92)Sb layer to a thickness of 1 μm; a second compound semiconductor layer: an Al_(0.3)In_(0.7)Sb layer to a thickness of 0.02 μm; and a third compound semiconductor layer having a second conductivity type: an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm. As line defect filter layers (a first B layer and a first D layer) to be inserted in the first compound semiconductor layer, three samples respectively using Al_(0.3)In_(0.7)Sb, Al_(0.15)Ga_(0.15)In_(0.7)Sb, and Ga_(0.3)In_(0.7)Sb were prepared (these samples will also be referred to as Examples 6a, 6b, and 6c, respectively).

As a sample to be compared, one sample was prepared with the following layers stacked in the stated order on a semi-insulating GaAs substrate to form a compound semiconductor layer:

an InSb layer to a thickness of 0.5 μm; a first compound semiconductor layer (a first A layer): an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm; a second compound semiconductor layer: an Al_(0.3)In_(0.7)Sb layer to a thickness of 0.02 μm; a light emitting layer: an Al_(0.08)In_(0.92)Sb layer to a thickness of 2 μm; a second compound semiconductor layer: an Al_(0.3)In_(0.7)Sb layer to a thickness of 0.02 μm; and a third compound semiconductor layer having a second conductivity type: an Al_(0.08)In_(0.92)Sb layer to a thickness of 0.5 μm.

The upper part of FIG. 6 and the upper part of FIG. 7 are cross-sectional TEM analysis results for the three samples in Example 6 and the sample to be compared.

The lower part of FIG. 6 and the lower part of FIG. 7 are tables indicating the line defect density (units: lines/cm²) of the light emitting layer obtained from the results of the plane-view TEM analysis on the three samples in Example 6 and the sample to be compared.

It can be seen from the analysis results in the upper part of FIG. 6 and the upper part of FIG. 7 that when any of Al_(0.3)In_(0.7)Sb, Al_(0.15)Ga_(0.15)In_(0.7)Sb, or Ga_(0.3)In_(0.7)Sb is used as the line defect filter layer, line defects are caused to bend in parallel to the plane direction of the GaAs substrate in the vicinity of the line defect filter layer, which fact provides the effect of reducing the line defect density of the layer above the line defect filter.

It is also confirmed from the line defect densities of the light emitting layers of the three samples presented in the lower part of FIG. 6 and the lower part of FIG. 7 that Al_(0.15)Ga_(0.15)In_(0.7)Sb (Example 6b) or Ga_(0.3)In_(0.7)Sb (Example 6c) can still provide the effect of reducing the line defect density of the light emitting layer when used as a line defect filter layer as in the case of using Al_(0.3)In_(0.7)Sb (Example 6a), and can still function as a line defect filter layer even if all or some of the Als are replaced with Ga.

It is understood that the effect of the present disclosure is also exhibited in the case of Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb in which all or some of the Als in Al_(x)In_(1-x)Sb are replaced with Ga.

<Measurement of Al Composition and Measurements of Composition of Elements other than Al of Each Layer>

TABLE 3 |n_(A12) + n_(Ga2) − |n_(A12) + n_(Ga2) − n_(A11A)/ n_(A11B)/ n_(A11C)/ |n_(A11B) + n_(Ga1B) − |n_(A11B) + n_(Ga1B) − n_(A12)/ (n_(A1 light) + (n_(A1 light) + n_(Ga1A) n_(Ga1B) n_(Ga1C) m_(1B) (n_(A11A) + n_(Ga1A))| (n_(A11A) + n_(Ga1A))| × m₂ n_(Ga2) n_(Ga light)) n_(Ga light))| × Example (%) (%) (%) (nm) (%) m_(1B) (nm) (%) (%) m₂ 6a 8/0 30/0  8/0 20 22 440 20 30/0 22 440 6b 8/0 15/15 8/0 20 22 440 20 30/0 22 440 6c 8/0  0/30 8/0 20 22 440 20 30/0 22 440

<Comparison of Quantum Emission Efficiency>

As a result of measuring the quantum emission efficiency in the samples of Examples 6a to 6c, it was confirmed that, when the quantum emission efficiency in Example 6a was taken as 100%, it was 93% in Example 6b in which some of the Als in Al_(x)In_(1-x)Sb in the line defect filter layer were replaced with Ga, and 99% in Example 6c in which all of the Als in Al_(x)In_(1-x)Sb in the line defect filter layer were replaced with Ga. In view of the above, even with a device using Ga_(x)In_(1-x)Sb or Al_(x-y)Ga_(y)In_(1-x)Sb in which all or some of the Als in Al_(x)In_(1-x)Sb were replaced with Ga for a line defect filter layer, it is possible to obtain high quantum emission efficiency and to further improve the emission intensity. 

1. An infrared light emitting device comprising: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer and containing at least In and Sb, where the light emitting layer has an Al composition at a proportion of n_(light) [%] in all group III elements in the light emitting layer where 0≤n_(light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n₂[%] in all group III elements in the second compound semiconductor layer where 0<n₂<100, and having a film thickness of m₂ [nm] where m₂>2, wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(1A) [%] in all group III elements in the first A layer where 0≤n_(1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(1B) [%] in all group III elements in the first B layer where 0≤n_(1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(1C) [%] in all group III elements in the first C layer where 0≤n_(1C)<18, where n_(1A), n_(1B), n_(1C), n₂, n_(light), m_(1B), and m₂ satisfy the following relations: |n ₂ −n _(light) |×m ₂ |n _(1B) −n _(1A) |×m _(1B); n _(1B) >n _(1A) and n _(1B) >n _(1C), or n _(1B) <n _(1A) and n _(1B) <n _(1C); and n ₂ >n _(light)+5.
 2. The infrared light emitting device according to claim 1, wherein n_(light), n_(1A), and n_(1C) satisfy the following relations: 8≤n _(light)≤12; 8≤n _(1A)≤12; and 8≤n _(1C)≤12.
 3. The infrared light emitting device according to claim 1, wherein n_(light), n_(1A), and n_(1C) satisfy the following relations: 4≤n _(light)≤8 4≤n _(1A)≤8; and 4≤n _(1C)≤8.
 4. The infrared light emitting device according to claim 1, wherein n₂, n_(light), and m₂ satisfy the following relation: |n ₂ −n _(light) |×m ₂≤441.
 5. The infrared light emitting device according to claim 1, wherein n_(light) and n₂ satisfy the following relation: n ₂ >n _(light)+7.
 6. The infrared light emitting device according to claim 1, wherein m₂ satisfies the following relation: m ₂≥5.
 7. The infrared light emitting device according to claim 1, wherein the first conductivity type is n type and the second conductivity type is p type.
 8. The infrared light emitting device according to claim 1, wherein infrared rays incident from the semiconductor substrate side are emitted.
 9. The infrared light emitting device according to claim 1, wherein n_(1A), n_(1C), and n_(light) are the same.
 10. The infrared light emitting device according to claim 1, wherein the second compound semiconductor layer is formed in both of regions between the light emitting layer and the third compound semiconductor layer and between the first compound semiconductor layer and the light emitting layer.
 11. An infrared light emitting device comprising: a semiconductor substrate; a first compound semiconductor layer formed on the semiconductor substrate and having a first conductivity type; a light emitting layer formed on the first compound semiconductor layer, containing at least In and Sb, and having an Al composition at a proportion of n_(Al light) [%] in all group III elements in the light emitting layer and a Ga composition at a proportion of n_(Ga light) [%] in all group III elements in the light emitting layer, where a sum of the proportions n_(Al light) and n_(Ga light) satisfies a relation of 0<n_(Al light)+n_(Ga light)<18; a third compound semiconductor layer formed on the light emitting layer and having a second conductivity type; and a second compound semiconductor layer formed in at least one of regions between the light emitting layer and the third compound semiconductor layer or between the first compound semiconductor layer and the light emitting layer, containing at least In, Al, and Sb, having an Al composition at a proportion of n_(Al2) [%] in all group III elements in the second compound semiconductor layer where 0≤n_(Al2)<100 and a Ga composition at a proportion of n_(Ga2) [%] in all group III elements in the second compound semiconductor layer where 0<n_(Ga2)<100, and having a film thickness of m₂ [nm] where m₂>2, wherein the first compound semiconductor layer comprises, in the stated order: a first A layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1A) [%] in all group III elements in the first A layer and a Ga composition at a proportion of n_(Ga1A) [%] in all group III elements in the first A layer, where a sum of the proportions n_(Al1A) and n_(Ga1A) satisfies a relation of 0<n_(Al1A)+n_(Ga1A)<18; a first B layer containing at least In and Sb, having an Al composition at a proportion of n_(Al1B) [%] in all group III elements in the first B layer and a Ga composition at a proportion of n_(Ga1B) [%] in all group III elements in the first B layer, where a sum of the proportions n_(Al1B) and n_(Ga1B) satisfies a relation of 0<n_(Al1B)+n_(Ga1B)<100, and having a film thickness of m_(1B) [nm]; and a first C layer containing at least In and Sb and having an Al composition at a proportion of n_(Al1C) [%] in all group III elements in the first C layer and a Ga composition at a proportion of n_(Ga1C) [%] in all group III elements in the first C layer, where a sum of the proportions n_(Al1C) and n_(Ga1C) satisfies a relation of 0<n_(Al1C)+n_(Ga1C)<18, where n_(Al1A), n_(Ga1A), n_(Al1B), n_(Ga1B), n_(Al1C), n_(Ga1C), n_(Al2), n_(Ga2), n_(Al light), n_(Ga light), m_(1B), and m₂ satisfy the following relations: |n _(Al2) +n _(Ga2)−(n _(Al light) +n _(Ga light))|×m ₂ |n _(Al1B) +n _(Ga1B)−(n _(Al1A) +n _(Ga1A))|×m _(1B); n_(Al1B)+n_(Ga1B)>n_(Al1A)+n_(Ga1A) and n_(Al1B)+n_(Ga1B)>n_(Al1C)+n_(Ga1C), or n_(Al1B)+n_(Ga1B)<n_(Al1A)+n_(Ga1A) and n_(Al1B)+n_(Ga1B)<n_(Al1C)+n_(Ga1C); n _(Al2) +n _(Ga2) >n _(Al light) +n _(Ga light)+5; 0<n _(Ga2)/(n _(Al2) +n _(Ga2))≤1; 0<n _(Ga light)/(n _(Al light) +n _(Ga light))≤1; 0<n _(Ga1A)/(n _(Al1A) +n _(Ga1A))≤1; 0<n _(Ga1B)/(n _(Al1B) +n _(Ga1B))≤1; and 0<n _(Ga1C)/(n _(Al1C) +n _(Ga1C))≤1.
 12. The infrared light emitting device according to claim 11, wherein n_(Al light), n_(Ga light), n_(Al1A), n_(Ga1A), n_(Al1C), and n_(Ga1C) satisfy the following relations: 8≤n _(Al light) +n _(Ga light)≤12; 8≤n _(Al1A) +n _(Ga1A)≤12; and 8≤n _(Al1C) +n _(Ga1C)≤12.
 13. The infrared light emitting device according to claim 11, wherein n_(Al light), n_(Ga light), n_(Al1A), n_(Ga1A), n_(Al1C), and n_(Ga1C) satisfy the following relations: 4≤n _(Al light) +n _(Ga light)≤8; 4≤n _(Al1A) +n _(Ga1A)≤8; and 4≤n _(Al1C) +n _(Ga1C)≤8.
 14. The infrared light emitting device according to claim 11, wherein n_(Al2), n_(Ga2), n_(Al light), n_(Ga light), and m₂ satisfy the following relation: |n _(Al2) +n _(Ga2)−(n _(Al light) +n _(Ga light))|×m ₂≤441.
 15. The infrared light emitting device according to claim 11, wherein n_(Al light), n_(Ga light), n_(Al2), and n_(Ga2) satisfy the following relation: n _(Al2) +n _(Ga2) >n _(Al light) +n _(Ga light)+7.
 16. The infrared light emitting device according to claim 11, wherein m₂ satisfies the following relation: m ₂≥5.
 17. The infrared light emitting device according to claim 11, wherein the first conductivity type is n type and the second conductivity type is p type.
 18. The infrared light emitting device according to claim 11, wherein infrared rays incident from the semiconductor substrate side are emitted.
 19. The infrared light emitting device according to claim 11, wherein n_(Al1A), n_(Al1C), and n_(Al light) are the same, and n_(Ga1A), n_(Ga1C), and n_(Ga light) are also the same.
 20. The infrared light emitting device according to claim 11, wherein the second compound semiconductor layer is formed in both of regions between the light emitting layer and the third compound semiconductor layer and between the first compound semiconductor layer and the light emitting layer. 